論文

The silicon cage nanoclusters encapsulating a tantalum atom, termed Ta@Si16, exhibit characteristics of alkali metal “superatoms (SAs)”. Despite this conceptual framework, the precise structures of Ta@Si16 and Ta@Si16+ remain unclear in quantum calculations due to three energetically close structural isomers: C3v, Td, and D4d structures. To identify the geometrical structure of Ta@Si16 SAs, structural analysis was conducted using extended X-ray absorption fine structure (EXAFS) with a high-intensity monochromatic X-ray source, keeping anaerobic conditions. Focusing on “superordered” films, which constitute amorphous thin films composed solely of Ta@Si16 SAs, this analysis preserved locally ordered structures. Spectral comparisons between experimental and simulated Ta L3-edge EXAFS unveil that Ta@Si16 SAs on a substrate adopt a C3v-derived structure, while Si K-edge EXAFS introduces spectral ambiguity in structural identifications, attributed to both intracluster and intercluster scatterings. These findings underscore the significance of locally ordered structure analyses in understanding and characterizing novel nanoscale materials.

Manganese-sulfur cluster anions (MnnSm-, n = 1-10, m = 1-10) have been studied using a magnetic-bottle type photoelectron spectroscopy (PES). The MnnSm- cluster anions were formed in a laser vaporization cluster source. The most stable cluster anions were found to have the compositions of n=m and n=m±1. The electron affinities of neutral manganese sulfide clusters were measured from the onsets of the PES spectra. A new electronically excited state at 0.75 eV above the ground state was found for MnS. From the size dependence of the PES spectra, it was found that Mn2S2-, Mn3S3-, and Mn4S4- are structural frameworks in MnnS2-, MnnS3-, and MnnS4- series, respectively. The electronic properties and geometrical structures of the clusters are discussed. © 1996 American Institute of Physics.

The electronic properties of alkanethiol self-assembled monolayers (alkanethiolate SAMs) associated with their molecular-scale geometry are investigated using scanning tunneling microscopy and spectroscopy (STM/STS). We have selectively formed the three types of alkanethiolate SAMs with standing-up, lying-down, and lattice-gas phases by precise thermal annealing of the SAMs which are conventionally prepared by depositing alkanethiol molecules onto Au(111) surface in solution. The empty and filled states of each SAM are evaluated over a wide energy range covering 6 eV above/below the Fermi level (E F) using two types of STS on the basis of tunneling current-voltage and distance-voltage measurements. Electronic states originating from rigid covalent bonds between the thiol group and substrate surface are observed near E F in the standing-up and lying-down phases but not in the lattice-gas phase. These states contribute to electrical conduction in the tunneling junction at a low bias voltage. At a higher energy, a highly conductive state stemming from the alkyl chain and an image potential state (IPS) formed in a vacuum gap appear in all phases. The IPS shifts toward a higher energy through the change in the geometry of the SAM from the standing-up phase to the lattice-gas phase through the lying-down phase. This is explained by the increasing work function of alkanethiolate/Au(111) with decreasing density of surface molecules. © 2012 American Chemical Society.

Chemical characterization was performed for an alkali-like superatom consisting of a Ta-encapsulating Si16 cage, Ta@Si16, deposited on a graphite substrate using X-ray photoelectron spectroscopy (XPS) to element-specifically clarify the local electronic structure of the cage atoms. The XPS spectra derived from Ta 4f and Si 2p core levels have been well modeled with a single chemical component, revealing the formation of a symmetric Si cage around the Ta atom in the deposited nanoclusters. On chemical treatments by heating or oxygen exposure, it is found that the deposited Ta@Si16 is thermally stable up to 700 K and is also exceptionally less reactive toward oxygen compared to other Ta-Si nanoclusters, although some heat degradation and oxidation accompany the treatments. These results show the promising possibility of applying Ta@Si16 as a building block to fabricate cluster-assembled materials consisting of naked nanoclusters.

Al13− and B@Al12− のアルミニウム超原子修飾基板の作成に成功

The geometric and electronic characteristics of phosphorus-atom doped aluminum nanoclusters, AlnPm (n = 7-17, m = 1 and 2), were investigated through a combination of experiments and theoretical calculations. The size dependences of the ionization energy (Ei) for AlnPm NCs exhibit a local minimum of 5.37 eV at Al12P1, attributed to an endohedral P@Al12 superatom (SA). This SA originates from an excess electron toward the 2P shell closing (40e), coexisting with an exohedral isomer featuring a vertex P atom. The stability of the endohedral P@Al12 is further enhanced in its cationic state compared to the exohedral isomer, when complexed with a fluorine (F) atom, forming an SA salt denoted as P@Al12+F- with an elevated Ei ranging from 6.42 to 7.90 eV. In contrast, for the anionic Al12P1-, the exohedral form is found to be more stable than the endohedral one using anion photoelectron spectroscopy and calculations. The geometric and electronic robustness of neutral P@Al12 SAs against electron donation and acceptance is discussed in comparison to rare-gas-like Si@Al12 SAs.

Laser-induced fluorescence of CO2+ (X̃ 2Πg) produced by electron impact on CO2 in a supersonic beam was measured. An analysis of the CO2+ (Ã-X̃) spectra has revealed that the rotational distribution of CO2+ is essentially Boltzmann and that the effective rotational temperature increases uniformly with decreasing impact energy, 26± 1 K at 300 eV and 31 ± 1 K at 45 eV. This trend of rotational excitation, which is similar to that observed in the N2 + e system, is interpreted in terms of the rotational transitions in electron-impact ionization. © 1988.

With the development of nanocluster (NC) synthesis methods in the gas phase, atomically precise NCs composed of a finite number of metal and semiconductor atoms have emerged. NCs are expected to be the smallest units for nanomaterials with various functions, such as catalysts, optoelectronic materials, and electromagnetic devices. The exploration of a stable NC called a magic number NC has revealed a couple of important factors, such as a highly symmetric geometric structure and an electronic shell closure, and a magic number behavior is often enhanced by mixing additional elements. A synergetic effect between geometric and electronic structures leads to the formation of chemically robust NC units called superatoms (SAs), which act as individual units assembled as thin films. The agglomeration of non-ligated bare SAs is desirable in fabricating the assembled SAs associated with intrinsic SA nature. The recent development of an intensive pulsed magnetron sputtering method opens up the scalable synthesis of SAs in the gas phase, enabling the fabrication of SA assembly coupled with the non-destructive deposition of a soft-landing technique. This perspective describes our recent progress in the investigation of the formation of binary cage SA (BCSA) assembled thin films composed of metal-atom encapsulating silicon-cage SAs (M@Si16) and germanium-cage SAs (M@Ge16), with a focus on their electrical properties associated with a conduction mechanism toward the development of new functional nanoscale materials.